CN106981371A - A kind of water system electrolyte super capacitance cell - Google Patents

A kind of water system electrolyte super capacitance cell Download PDF

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Publication number
CN106981371A
CN106981371A CN201610026074.1A CN201610026074A CN106981371A CN 106981371 A CN106981371 A CN 106981371A CN 201610026074 A CN201610026074 A CN 201610026074A CN 106981371 A CN106981371 A CN 106981371A
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electrolyte
zinc
water
capacitance cell
battery
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黄潮
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黄潮
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/58Liquid electrolytes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention discloses a kind of water system electrolyte super capacitance cell, including positive pole, negative pole, electrolyte, positive pole uses the carbon material with super capacitor property for active material, and negative pole uses zinc for electrode active material, and electrolyte is more than 2.5 aqueous solution using pH;Belong to electrochemical energy storage field, it is low with cost, have extended cycle life, power density is big, the characteristics of energy density ratio is higher, it is adaptable to the high power energy storage such as wind energy, the energy storage of solar energy and power network and startup power supply.

Description

A kind of water system electrolyte super capacitance cell
Technical field
The present invention relates to electrochemical energy storage field, more particularly to a kind of water system electrolyte super capacitance cell.
Background technology
With economic development and the deterioration of environment, it is necessary to gradually substitute fossil energy, but the wind energy sun with regenerative resource There is intermittent and randomness, large-scale use can impact power network, and good energy storage technology is not with regard to nothing the regenerative resources such as energy more Method is connected to the grid large-scale use;Power consumption is very big with the fluctuation of time in the power network of the compositions such as thermal power generation, if big rule The method balance peak valley of mould storing up electricity, just can be greatly reduced installed capacity, obtain obvious benefit;Extensive energy storage is intelligent electricity The key technology of net and New Energy Industry.
Energy storage technology mainly has mechanical energy storage, Power Flow, electrochemical energy storage and phase-change accumulation energy four major types.Technology maturation application It is water-storage in mechanical energy storage to compare wide, and its energy-accumulating power station accounts for the 3% of global capacity of installed generator, and energy density is low, The reservoir of large area is needed, is limited by geographical conditions.Electrochemical energy storage applicability of secondary batteries realizes the conversion of electric energy and chemical energy, Energy storage density is high, and response is fast, flexibly and easily, very promising not by geographical and size limit.
General secondary cell cycle life tens to thousands of times, energy density be tens to several hectowatts hour/kilogram(Wh/kg), Watt/kilogram of power density 300(W/kg)Below.Conventional secondary cell has lead-acid battery, Ni-MH battery, lithium ion battery;Lead Sour battery price is cheap, is widely used in starting, the field such as stand-by power supply, and it has the disadvantage that energy density is not high, deep discharge ability, Cycle life is limited, and the lead contamination caused is still serious environmental problem;Ni-MH battery power density ratio is larger, and economy is remote Not as lead-acid battery, there is certain memory effect, can only be applied in less field;Lithium ion battery energy density is high, memoryless Effect, has extended cycle life, and in portable electronic device field, application is extremely wide, but cost is high, consistency of battery pack during large-scale application The safety problem that difference, organic electrolyte and lithium are brought also limit its large-scale application.
Flow battery is a kind of secondary cell of special shape, by the oxidant or reducing agent of both positive and negative polarity reactant with dissolved form In the presence of the discharge and recharge on inert electrode is strong with deep discharge ability typically with pump circulation, the characteristics of having extended cycle life;According to negative The difference of pole reducing agent and positive pole oxidant, there is all-vanadium flow battery, zinc-bromine flow battery, sodium polysulfide-bromine flow battery, iron A variety of flow battery forms such as chrome liquor galvanic battery.By the research and development of decades, current all-vanadium flow battery, zinc-bromine flow battery is just Attempting large-scale commercial application.All-vanadium flow battery investment is big, it is necessary to which expensive fluoride ion exchanges barrier film, V electrolyte Not only cost is high but also preparation technology requirement is tight;The vanadic anhydride that the positive pole liquid of also anode electrolyte leakage is produced after air-drying Hypertoxic the problem of, is difficult to solve.The economic performance of zinc-bromine flow battery is good, but positive pole bromine corrosion power is extremely strong, and human and environment is endangered The big problem of evil limits its application.
Sodium-sulfur secondary battery works in 350 degrees centigrades, and production cost is relatively low, and energy density is high, and power density is big;Running temperature The long-time stability of high and resistant to elevated temperatures solid electrolyte are the technology barriers for being difficult in its stored energy application overcome.
In high power energy storage field, such as automobile starting, the application such as hybrid power, the power of general secondary cell, cycle performance are all Shortcomings, and the performance of the supercapacitor for being based primarily upon " electric double layer energy storage mechnism " is protruded, its power density reaches battery 10-100 times, cycle life reaches 100,000 times, memory-less effect, resistance to deep discharge and recharge.Being adopted current commercialized ultracapacitor more With symmetric form, the electrode of two identical materials, equivalent to two electric capacity series connection, the quality specific capacitance phase of whole electric capacity are used When a quarter of the specific capacitance in single electrode, energy density is small, typically only 1Wh/kg to 5Wh/kg or so, economic performance Difference, same capacity price is 5 times of lithium ion battery or so, limits its large-scale application.
Composite super capacitor is constituted with the single electrode of super capacitor and the single electrode of battery, or is super capacitance cell, It is a kind of special electrochemical energy storage cell form, combines super capacitor electrode power height, cycle life extremely long and battery electricity The characteristics of pole energy density is high.
It is positive pole with activated carbon, graphite is negative pole, carbon lithium super capacitance cell is constituted in the organic electrolyte containing lithium ion, When the electric double layer capacitance of anode activated charcoal carries out discharge and recharge, embedded abjection reaction of the lithium ion on graphite, voltage occur for negative pole Height, energy density is far above the ultracapacitor of symmetric form;But organic electrolyte cost is high, working condition is harsh, activated carbon Electrode is higher by tens times of super capacitor special-purpose activated charcoals for arriving hundred times with than general commercial activated carbons price so that organic The commercialization of electrolyte super capacitance cell is difficult.
Water system electrolyte cost is low, safe and reliable, but water system electrolyte super capacitance cell still has many problems at present;Than Such as using nickel electrode as positive pole, porous carbon is high for the nickel carbon capacitor batteries cost of negative pole;Using lead dioxide electrode as positive pole, activated carbon is The lead of negative pole-carbon capacitor batteries positive pole is easy to fall off, there is lead and sulfate pollution.It is electrolysed with the water system of secondary battery extremely negative pole A kind of considerably less, Chinese patent " hybrid super capacitor and its manufacture method " (publication number of matter super capacitance cell research CN101515507A), one kind is disclosed using double-layer capacitor carbon material or with pseudo-capacitance elastomeric material as positive pole, hydrogen storage Alloy is the aqueous super capacitor batteries of negative pole, and its voltage is relatively low, it is necessary to using hydrogen bearing alloy, be operated in concentrated alkaline electrolyte In.
In energy storage field, in the urgent need to economic performance is good, have extended cycle life, deep discharge ability is strong, power density is big, energy density Compare high, the electrochemical energy storage method without environmental pollution, existing electrochemical energy storage technology can not meet requirement.
The content of the invention
The object of the invention is high in the existing electrochemical energy storage method cost of solution, and cycle performance is poor, and power density is low, and energy storage is close Degree is small, the problem of polluting environment.
Technical scheme proposed by the present invention is:A kind of water system electrolyte super capacitance cell, including positive pole, negative pole and electrolyte, It is characterized in that positive pole uses the carbon material with super capacitor property for active material, negative pole uses zinc for electrode activity thing Matter, electrolyte is more than 2.5 aqueous solution using pH.
The super capacitance cell positive pole of the present invention is based primarily upon " electric double layer capacitance mechanism ", and the redox reaction of zinc occurs for negative pole Coordinate with positive pole:During charging, positive pole loses electronics by external circuit, the surface charge of electrode attract the anion in electrolyte and Cation in electrolyte is repelled to form electric double layer capacitance;Negative pole obtains the divalent zinc in electronics, electrolyte by external circuit Ion generation metallic zinc is deposited on electrode;During electric discharge, positive pole obtains electronics by external circuit, and the surface charge of electrode attracts electricity Solve the cation in matter and the anion in electrolyte is repelled to form electric double layer capacitance;Negative pole loses electronics by external circuit, Metallic zinc on electrode, which loses, is electronically generated divalent zinc dissolving in the electrolyte, so circulation.
Carbon material with super capacitor property, refer to porous carbon materials for example activated carbon, NACF, multidimensional graphite material, The combination of carbon aerogels, CNT, treated glass carbon material, graphene etc. or above carbon material;From economy Property consider, preferred absorbent charcoal material.
Negative pole is electrode active material using zinc, refers to using metallic zinc and its oxidation product divalent zinc, such as metal zinc, electricity are heavy The divalent zinc of product metallic zinc on a current collector, zinc oxide either in solution for electrode active material or the above combination.
Negative pole can also directly use zinc metal sheet, using metal zinc metal sheet as active material and collector.
Water system electrolyte refers to electrolyte using water as entirely or essentially solvent, and solute can contain zinc ion for electrode active material;It is molten Matter electrolyte can be the various electrolyte such as acid, salt, alkali or its combination, can also add part regulation freezing point other are molten Agent, such as alcohols as ethylene glycol, glycerine.
In weak acid, neutrality, weak base compared with temperate condition, zinc electro-deposition is than more uniform, while stable beneficial to electrode and component;As It is preferred that, electrolyte pH of the invention is within 4 to 10.
Potassium ion, sodium ion, ammonium ion, lithium ion, chlorion, sulfate ion, nitrate ion can be contained in electrolyte Etc. readily soluble composition or its combination;Chlorion is soluble in water, and conductive capability is strong, and cost is low, and the present invention preferably chloride ion-containing concentration exists More than 0.5mol/L electrolyte.
Preferably, the complexing agent of zinc or the complexing composition containing zinc can be added in electrolyte, such as ammonia or ammonium, citric acid, gelatin, Dextrin, flour, starch etc.;When having the complexing agent of zinc in the electrolytic solution, zinc ion concentration reduces, and increases the uniform of zinc electro-deposition Property, it is to avoid produce zinc dendrite;Zinc electrode current potential is reduced, and increases cell voltage;The network of complexing agent or zinc of the present invention preferably containing zinc Synthesize the electrolyte of part.
Preferably, containing ammonium ion or the ammonia of complex state or the two combination, ammonium ion and complexing in the electrolyte of the present invention The ammonia total concentration of state is in more than 0.5mol/L.
Preferably, containing citrate in the electrolyte of the present invention, its total concentration is in more than 0.1mol/L.
Preferably, composition such as indium, bismuth, tin, the lead and other elements for suppressing zinc liberation of hydrogen can be added in electrolyte or in negative pole.
There are electrolytes to open composition battery in the middle of positive pole and negative pole;Leaching electrolyte can be inhaled using electrolyte barrier film to bear positive pole Pole is separated, such as with traditional polyethylene battery barrier film, polypropylene battery diaphragm, pulp layered paper etc.;It can also make without using barrier film The dividing plate or bulkhead for having space with centre separate positive pole negative pole.
Only positive pole negative pole can be separated with gel state electrolyte, starch gel is such as used without using barrier film, dividing plate or bulkhead Glue.
Except using electrolyte sleep mode, electrolyte flow mode can also be used, electrolyte continuous stream is promoted with mechanical force Dynamic or intermittent flow;In the form of flowing electrolyte, electrode polarization can be greatly reduced, it is to avoid zinc dendrite, it is to avoid bubbing is accumulated It is tired, power can be increased with high current density discharge and recharge.
Beneficial effects of the present invention
Porous carbon materials such as activated carbon, higher than face value, electric double layer capacitance is very big, and what is be made just has super capacitor electrode Good reversibility, power is big, the characteristics of life-span is extremely long.Zinc is a kind of cheap high-energy-density electrode active material;In standard state Under, zinc electrode current potential is lower than hydrogen 0.763 volt, and overpotential of hydrogen evolution is high.Zinc electrode is widely used in aqueous electrolyte cell, electricity Current density is high, and invertibity is relatively good.The present invention coordinates porous carbon positive pole and zinc load, constitutes aqueous super capacitor batteries, can With the special-purpose activated charcoal of the organic electrolyte ultracapacitor of inexpensive using general cheap absorbent charcoal material, economic performance It is better than lead-acid battery, cycle life is more than 6000 times, and power density exceedes general battery, water of the energy density close to general battery It is flat;Using the carbon material of bigger specific capacitance value, energy density reaches the level of general battery;Material therefor aboundresources, no dirt Dye;It can be widely applied to wind and solar energy and power network energy storage and start the fields such as stand-by power supply.
The water system electrolyte super capacitance cell of the present invention has advantages below:
The zinc load that the low use single electrode super capacitor carbon positive pole of 1 cost coordinates energy storage density high and is dirt cheap, battery cost The mainly cost of carbon material, the general absorbent charcoal material that cheap business can be used largely to produce, substantially reduce it is overall into Originally, zinc electrode, aqueous electrolyte, barrier film, component can use cheap material.
2 good cycle super capacitor electrode cycle life itself are 100,000 times of general battery, basic with solvable in divalent zinc Under conditions of state is present, the zinc electrode life-span is extremely long;Complexing agent can also be coordinated, the conditions, integral battery door longevity such as electrolyte is flowed Life is considerably beyond general electrode, and deep discharge ability is strong, memory-less effect.
The big super capacitor electrode current density of 3 power densities reaches a hundred or so times of general battery, its oxidation product divalent zinc with Solvable state is present, and the current density of zinc electrode can reach considerably beyond general battery electrode during the condition such as electrolyte flow 100 milliamps per square centimeter(mA/cm2).
4 energy densities are greatly improved because the quality specific capacitance of single electrode is 4 times of integrated symmetric capacitor specific capacitance, and is adopted Coordinate the low zinc load of energy storage density high electrode current potential with single electrode super capacitor positive pole so that the work of capacitor batteries of the invention Make voltage significantly more than the symmetrical super capacitor of general water system, zinc electrode accounts for the very fraction of battery quality, energy density is main It is decided by carbon material, it is ensured that it is higher by 10 times or so of the symmetrical super capacitor of water system, can reach the energy density of battery.
5 materials enrich pollution-free, Carbon Materials, zinc electrode, water system electrolyte, barrier film, and component all can be using pollution-free nonhazardous Material, and aboundresources
Embodiment
Electrode will be made together with the processing of electrode active material and collector using the various methods in general battery process, such as Using apply cream, be pressed into, electro-deposition or the method burnt till;Electrode active material and collector can be bonded with binding agent, can To add conductive agent increase conductance, method can be machined into and coordinated such as hot pressing, roll-in, etc..
The binding agent is the one or more in Kynoar, butadiene-styrene rubber, polytetrafluoroethylene (PTFE).
The conductive agent is the one or more in acetylene black, conductive black, graphite powder, CNT, graphene.
Collector can use metal such as titanium etc.;Various carbon materials such as graphite etc. can be used;Carbon material can be used with polymerizeing The composite of thing such as carbon black, acetylene black, graphite and plastics or rubber combined material;It can use conductive plastics, or with On combination.
Example 1
Positive active material uses commercially available chemical reagent-grade activated carbon, and conductive agent is acetylene black, and binding agent is Kynoar (PVDF), use 1-METHYLPYRROLIDONE(NMP)For PVDF solvent;By activated carbon:Acetylene black:Binding agent=83:12:5(Quality Than)Mix, add a little NMP and stir evenly into film slurries;Long 6.0cm is used, wide 1.0cm titanium sheet is collector, and slurry is coated in Titanium sheet collector is close at the 1.0cm of bottom, area 1.0cm2, it is dry to be fabricated to positive pole.
Negative pole is long 6.0cm, wide 1.0cm pure zinc metal sheet;Electrolyte is containing 20.0% ammonium chloride, 12.0% zinc chloride, 5.0% chlorination Potassium(Mass concentration)The aqueous solution.
Using the battery clamp of filter-press cell structure, in set electrolyte flow channel;5mm is cut out in the middle of the thick rubber slabs of 5mm The 1 cm2 spaces in wide hollow duct and electrode reaction area, distinguish frame in the both sides of runner, with this by positive plate negative plate Between rubber separator with hollow duct and electrode reaction area separate both positive and negative polarity, without using electrode diaphragm;With being drilled with runner hole and spiral shell The thick lucite of the two panels 7mm of rod aperture is end plate, plugs screw rod, and tightening nut clamps positive plate, the rubber slab with runner, born Pole piece.
It is passed through with constant flow pump after electrolyte, electrolyte does not flow;Discharge and recharge, 5mA/cm are controlled with battery analyzer2Constant-current charge To 1.70 volts, 5mA/cm2Constant-current discharge is to 0.40 volt, iterative cycles.Current efficiency 100%, energy efficiency 81.0%, by activated carbon Mass Calculation, specific capacitance value reaches 47.2 farads/gram(F/g), energy density reaches 13.7Wh/kg, and 6000 capacity of circulation are not Become.
Example 2
Positive active material uses commercially available chemical reagent-grade activated carbon, and conductive agent is acetylene black, and binding agent is polytetrafluoroethylene (PTFE) (PTFE), the PTFE emulsion of mass concentration 60% is first diluted into 5 times of additions with ethanol;By activated carbon:Acetylene black:Binding agent=80: 15:5(Mass ratio)Mix, add ethanol wet and stir evenly, with roll-in legal system cathode film, dry, with tablet press machine with 10MPa pressure pressures Film, is attached on titanium sheet collector, is made as positive pole.
Without using electrode diaphragm, using the battery clamp of filter-press cell structure, in set electrolyte flow channel;Negative pole is pure zinc Piece;Electrolyte is containing 18.0% ammonium chloride, 30.0% zinc chloride(Mass concentration)The aqueous solution.
Electrolyte is passed through, electrolyte is promoted with 100 cm per minutes with constant flow pump(cm/min.)Line flow rate;Surveyed with battery Determine instrument control discharge and recharge, 100mA/cm2Constant-current charge is to 2.0 volts, 100mA/cm2Constant-current discharge is to 0.1 volt, iterative cycles.Electric current Efficiency 99% to 100%, energy efficiency 51.5% or so, by activated carbon Mass Calculation, power density reaches 1058W/kg, than electricity Capacitance reaches 35.5F/g, and energy density reaches 8.1Wh/kg, and 500 capacity of circulation are constant.
Example 3
Positive active material uses high iodine number activated carbon, and conductive agent is acetylene black, and binding agent is polytetrafluoroethylene (PTFE)(PTFE), will The PTFE emulsion of 60% mass concentration first dilutes 5 times of additions with ethanol;By activated carbon:Acetylene black:Binding agent=80:15:5(Quality Than)Mix, add ethanol wet and stir evenly, with roll-in legal system cathode film, dry, titanium is attached to 10MPa pressure press molds with tablet press machine On piece collector, positive pole is made as.
Without battery diaphragm, using the battery clamp of filter-press cell structure, in set electrolyte flow channel;Negative pole is pure zinc Piece;29.0% ammonium chloride, the aqueous solution of 9.0% zinc chloride are taken, adjusts pH to be 8.00 with strong caustic, adjusts ultimate density For 14.5% ammonium chloride, 4.5% zinc chloride(Mass concentration), using this solution as electrolyte.
Electrolyte after electrolyte is passed through not flow;Discharge and recharge, 10mA/cm are controlled with battery analyzer2Constant-current charge to 1.57 volts, 10mA/cm2Constant-current discharge is to 0.33 volt, iterative cycles.Current efficiency 100%, energy efficiency 69.5%, based on activated carbon quality Calculate, specific capacitance value reaches 196.3F/g, energy density reaches 50.9Wh/kg, and 600 capacity of circulation are constant.
Example 4
High iodine number wood activated charcoal during positive active material is used, conductive agent is acetylene black, and binding agent is polytetrafluoroethylene (PTFE) (PTFE), the PTFE emulsion of 60% mass concentration is first diluted into 5 times of additions with ethanol;By activated carbon:Acetylene black:Binding agent=80: 15:5(Mass ratio)Mix, add ethanol wet and stir evenly, with roll-in legal system cathode film, dry, with tablet press machine with 10MPa pressure pressures Film is attached on titanium sheet collector, is made as positive pole.
Without battery diaphragm, using the battery clamp of filter-press cell structure, in set electrolyte flow channel;Negative pole is pure zinc Piece;Electrolyte is containing 16.8% potassium hydroxide, 1.2% zinc oxide(Mass concentration)The aqueous solution.
Electrolyte after electrolyte is passed through not flow;Discharge and recharge, 10mA/cm are controlled with battery analyzer2Constant-current charge to 1.65 volts, 10mA/cm2Constant-current discharge is to 0.40 volt, iterative cycles.By activated carbon Mass Calculation, specific capacitance value reaches 77.6F/g, and energy is close Degree reaches 20.3Wh/kg, and current efficiency 98.5% or so, energy efficiency 77.8%, 500 capacity of circulation are basically unchanged.
Example 5
Positive active material uses commercially available chemical reagent-grade activated carbon, and conductive agent is acetylene black, and binding agent is polytetrafluoroethylene (PTFE) (PTFE), the PTFE emulsion of 60% mass concentration is first diluted into 5 times of additions with ethanol;By activated carbon:Acetylene black:Binding agent=80: 15:5(Mass ratio)Mix, add ethanol wet and stir evenly, with roll-in legal system cathode film, dry, with tablet press machine with 10MPa pressure pressures On titanium sheet collector, positive pole is made as.
Without battery diaphragm, using the battery clamp of filter-press cell structure, in set electrolyte flow channel;Negative pole is pure zinc Piece;Electrolyte is 3% citric acid, 25% ammonium chloride, 3% zinc chloride, 0.005% indium sulfate(Mass percent)The aqueous solution.
Electrolyte after electrolyte is passed through not flow;Discharge and recharge, 5mA/cm are controlled with battery analyzer2Constant-current charge to 1.70 volts, 5mA/cm2Constant-current discharge is to 0.40 volt, iterative cycles.By activated carbon Mass Calculation, specific capacitance value reaches 49.8F/g, and energy is close Degree reaches 12.8Wh/kg, and current efficiency 100%, energy efficiency 75.3%, 1500 capacity of circulation are basically unchanged.
Example 6
High iodine number activated carbon during positive active material is used, conductive agent is acetylene black, and binding agent is Kynoar(PVDF), Use 1-METHYLPYRROLIDONE(NMP)For PVDF solvent;By activated carbon:Acetylene black:Binding agent=83:12:5(Mass ratio)Mix, Add a little NMP and stir evenly into film slurries;Slurry is coated in titanium sheet collector close at the 1cm of bottom, area 1.0cm2, dry It is fabricated to positive pole.
Negative pole is the titanium sheet of electrogalvanizing;Separate both positive and negative polarity using battery diaphragm, battery diaphragm is the poly- of outsourcing polypropylene non-woven fabric Vinyl Graft film, electrolyte is 5.0% potassium chloride, 20.0% ammonium chloride, 12.0% zinc chloride, 0.005% indium sulfate(Mass concentration) The aqueous solution.
Discharge and recharge, 10mA/cm are controlled with battery analyzer2Constant-current charge is to 1.70 volts, 10mA/cm2Constant-current discharge to 0.40 volt, Iterative cycles.By activated carbon Mass Calculation, specific capacitance value reaches 101.0F/g, and energy density reaches 17.3Wh/kg, current efficiency 100%, energy efficiency 60.7%, 560 capacity of circulation are constant.
Example 7
High iodine number activated carbon during positive active material is used, conductive agent is acetylene black, and binding agent is Kynoar(PVDF), use 1-METHYLPYRROLIDONE(NMP)For PVDF solvent;By activated carbon:Acetylene black:Binding agent=83:12:5(Mass ratio)Mix, plus Enter a little NMP and stir evenly into film slurries;Slurry is coated in titanium sheet collector close at the 1.0cm of bottom, area 1.0cm2, dry system It is made positive pole.
Negative pole is pure zinc metal sheet;Take 5.0% potassium chloride, 20.0% ammonium chloride, 12.0% zinc chloride(Mass concentration)The aqueous solution 10.0 Gram, the starch of 1.5 grams of addition is stirred evenly, heating water bath insulation gelatinization, forms the starch hydrogel containing electrolyte;By positive pole negative pole Piece is inserted respectively, is electrolytes positive pole negative pole with this starch hydrogel, without battery diaphragm.
Discharge and recharge, 5mA/cm are controlled with battery analyzer2Constant-current charge is to 1.70 volts, 5mA/cm2Constant-current discharge is to 0.40 volt, instead Multiple circulation.By activated carbon Mass Calculation, specific capacitance value reaches 149.4F/g, and energy density reaches 45.1Wh/kg, current efficiency 97.4% to 100%, energy efficiency 81.1% or so, 500 capacity of circulation are basically unchanged.
Embodiment described above is the preferred version of the present invention, does not make any formal limitation to the present invention, not It can also be implemented with other forms on the premise of the technical scheme described in claim.

Claims (10)

1. a kind of water system electrolyte super capacitance cell, including positive pole, negative pole, electrolyte, it is characterised in that:The positive pole is used Carbon material with super capacitor property is active material, and the negative pole uses zinc for electrode active material, and the electrolyte is adopted It is more than 2.5 aqueous solution with pH.
2. water system electrolyte super capacitance cell as claimed in claim 1, it is characterised in that:The positive pole use activated carbon for Active material.
3. water system electrolyte super capacitance cell as claimed in claim 1, it is characterised in that:The pH value of the electrolyte is 4 To within 10.
4. water system electrolyte super capacitance cell as claimed in claim 1, it is characterised in that:In the electrolyte containing chlorine from Son, chlorine ion concentration >=0.5mol/L.
5. water system electrolyte super capacitance cell as claimed in claim 1, it is characterised in that:Contain zinc in the electrolyte Complexing agent or the complexing composition containing zinc.
6. water system electrolyte super capacitance cell as claimed in claim 1, it is characterised in that:Contain ammonium ion in the electrolyte Or complex state ammonia or its combination, ammonium ion and complex state ammonia total concentration >=0.5mol/L.
7. water system electrolyte super capacitance cell as claimed in claim 1, it is characterised in that:Contain lemon in the electrolyte Acid group, its total concentration >=0.1mol/L.
8. water system electrolyte super capacitance cell as claimed in claim 1, it is characterised in that:The electrolyte uses flowing side Formula.
9. aqueous super capacitor batteries as claimed in claim 1, it is characterised in that:The electrolyte is electrolysed using gel state Liquid.
10. aqueous super capacitor batteries as claimed in claim 1, it is characterised in that:In the electrolyte or negative pole add indium, Bismuth, tin, the liberation of hydrogen inhibitor that the one or more of lead and other elements are zinc.
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CN108538634A (en) * 2018-05-25 2018-09-14 北京化工大学 A kind of water system compounding electrolyte and its preparation method and application
CN109524248A (en) * 2018-12-06 2019-03-26 中国科学院兰州化学物理研究所 A kind of construction method of zinc ion mixed capacitor
CN109786861A (en) * 2019-01-17 2019-05-21 中国科学院上海硅酸盐研究所 A kind of hybrid electrochemical energy storage device
CN111370783A (en) * 2020-04-08 2020-07-03 大连理工大学 High-performance water-based chloride ion battery and preparation method thereof
WO2020147635A1 (en) * 2018-01-17 2020-07-23 Chao Huang Aqueous hybrid super capacitor

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CN103560019B (en) * 2013-10-30 2016-05-04 中国第一汽车股份有限公司 A kind of zinc ion hybrid super capacitor

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CN108538634A (en) * 2018-05-25 2018-09-14 北京化工大学 A kind of water system compounding electrolyte and its preparation method and application
CN109524248A (en) * 2018-12-06 2019-03-26 中国科学院兰州化学物理研究所 A kind of construction method of zinc ion mixed capacitor
CN109786861A (en) * 2019-01-17 2019-05-21 中国科学院上海硅酸盐研究所 A kind of hybrid electrochemical energy storage device
CN111370783A (en) * 2020-04-08 2020-07-03 大连理工大学 High-performance water-based chloride ion battery and preparation method thereof

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